EP0757032A2 - Composé naphtalénique, et composition et élément cristal liquide le contenant - Google Patents

Composé naphtalénique, et composition et élément cristal liquide le contenant Download PDF

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Publication number
EP0757032A2
EP0757032A2 EP96304958A EP96304958A EP0757032A2 EP 0757032 A2 EP0757032 A2 EP 0757032A2 EP 96304958 A EP96304958 A EP 96304958A EP 96304958 A EP96304958 A EP 96304958A EP 0757032 A2 EP0757032 A2 EP 0757032A2
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liquid crystal
natural number
carbon atoms
naphthoate
ethyl
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EP0757032B1 (fr
EP0757032A3 (fr
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Tsutomu Ishida
Atsuo Otsuji
Yoshiyuki Totani
Motokazu Hirao
Hiroe Kayashima
Masakatsu Nakatsuka
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Mitsui Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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Priority to EP01106687A priority patent/EP1120400B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0225—Ferroelectric
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine

Definitions

  • the present invention relates to naphthalene compounds, liquid crystal compositions containing naphthalene compounds, and a liquid crystal element using such a liquid crystal composition.
  • Liquid crystal display elements have so far widely been used for various display elements by making the best use of excellent characteristics thereof such as low voltage actuation, low power consumption, possibility of thin type display, and no fatigue of eyes because of light-receptive display element.
  • TN twisted nematic
  • STN super twisted nematic
  • These display elements are nematic liquid crystal display elements using nematic liquid crystal.
  • These nematic liquid crystal display elements have the defect that they have a long response time and therefore can provide only a response time falling in an order of some ten msec.
  • liquid crystal elements A recent progress in industrial techniques has been followed by strong requirement of high speed response to liquid crystal elements, and in order to meet such requirement, various attempts have been made by improving liquid crystal materials.
  • a display device making use of a photoswitching phenomenon of ferroelectric liquid crystal has been proposed [Appl. Phys. Lett., 36 , 899 (1980)].
  • the liquid crystal elements are expected to be applied to not only displays for liquid crystal televisions, etc., but also to materials for optoelectronics-related elements such as optical printer heads, optical Fourier transform elements and light valves.
  • Ferroelectric liquid crystals belong to tilt series chiral smectic phases in terms of a liquid crystal phase, and among them, liquid crystal phase called a chiral smectic C phase having a low viscosity is preferred from a viewpoint of practical use.
  • liquid crystal phase called a chiral smectic C phase having a low viscosity is preferred from a viewpoint of practical use.
  • Various liquid crystal compounds showing chiral smectic C phases have so far been investigated, and a lot of compounds have already been found and produced. Conditions for using them for ferroelectric liquid crystal elements include:
  • ferroelectric liquid crystal compositions obtained by blending several liquid crystal compounds or non-liquid crystal compounds have to be used in practical uses.
  • a ferroelectric liquid crystal composition does not always comprise only ferroelectric liquid crystal compounds, and it is disclosed in, for example, Japanese Patent Application Laid-Open No. 60-36003 (1985) that compositions showing ferroelectric liquid crystal phases as a whole can be obtained by employing compounds or compositions showing non-chiral smectic C, F, G, H and I phases for fundamental materials and blending them with one or plural compounds showing ferroelectric liquid crystal phases. Further, it is reported that ferroelectric liquid crystal compositions can be obtained as a whole by employing compounds or compositions showing phases such as a non-chiral smectic C phase for fundamental materials and blending them with one or plural compounds which are optically active but do not show ferroelectric liquid crystal phases [Mol. Cryst. Liq. Cryst., 89, 327 (1982)].
  • Phenylpyrimidine series liquid crystal compounds and phenylbenzoate series liquid crystal compounds as shown below have so far been known as typical compounds showing chiral smectic C phases: wherein R represents an alkyl group, and R* represents an optically active alkyl group.
  • naphthalene series liquid crystal compounds as shown below are proposed in Japanese Patent Application Laid-open No. 63-246346 (1988), Japanese Patent Application Laid-open No. 1-193390 (1989), Japanese Patent Application Laid-open No. 3-68686 (1991) and Japanese Patent Application Laid-open No. 3-106850 (1991): wherein R represents an alkyl group, and R* represents an optically active alkyl group.
  • ferroelectric liquid crystal compositions using the phenylpyrimidine series liquid crystal compounds or phenylbenzoate series liquid crystal compounds described above have had the problems that they are liable to cause orientation unevenness so as to bring about defects when they are put into liquid crystal cells and that the good memory property can not be obtained and the contrast ratio is low.
  • ferroelectric liquid crystal compositions comprising the naphthalene series compounds described above show good orientation when liquid crystal cells are charged with them, and can provide a good memory property without having defects.
  • Preferred embodiments of the invention may provide liquid crystal compounds suited to improve such various characteristics as high speed response, orientation and high contrast ratio when the liquid crystal compound is blended into a ferroelectric liquid crystal composition in order to put a ferroelectric liquid crystal element into practical use, a compound useful as a component for a liquid crystal composition, an intermediate product for producing the above compound and a liquid crystal composition containing the above compound, and a liquid crystal element using said liquid crystal composition.
  • the present invention relates to a naphthalene compound represented by the following Formula (1): wherein R 1 and R 2 each represent a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which may be substituted with halogen atoms and have no asymmetric carbon atoms;
  • A represents any of the groups represented by the following formulas: (wherein X 1 , X 2 , X 3 and X 4 each represent a hydrogen atom or a halogen atom, and 1,4-cyclohexylene ring is disposed in a trans position); and z represents 0 or 1.
  • the present invention relates to a naphthalene compound represented by the following Formula (2) which is useful as an intermediate product when producing the naphthalene compound represented by Formula (1): wherein R 3 represents a branched alkyl group having no asymmetric carbon atoms and having 3 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which are substituted with halogen atoms and have no asymmetric carbon atoms; and B 1 represents a hydrogen atom or a benzyl group.
  • R 3 represents a branched alkyl group having no asymmetric carbon atoms and having 3 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which
  • the present invention relates to a liquid crystal composition using the compound represented by Formula (1), and a liquid crystal element using said liquid crystal composition.
  • the liquid crystal composition using the naphthalene compound of the preferred embodiments is improved in various characteristics such as high speed response, temperature dependency of a response time, etc.
  • Fig. 1 is a schematic, cross-sectional view of one example of a liquid crystal element using a liquid crystal showing a chiral smectic phase.
  • Fig. 2 is a graph showing the temperature dependency of the response time of the liquid crystal compositions of Examples 115 and 116 and the comparative example.
  • the naphthalene compound of the present invention represented by Formula (1) is a novel compound.
  • R 1 and R 2 each represent a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which may be substituted with halogen atoms and have no asymmetric carbon atoms.
  • R 1 and R 2 each represent a linear or branched alkyl group represented by Formulas (I) and (II): -C a H 2a+1 (n) (I) -(CH 2 ) b CH(C c H 2c+1 ) 2 (II) (wherein a represents a natural number of 1 to 20; b represents a natural number of 0 to 17; and c represents a natural number of 1 to 9, provided that b +(c ⁇ 2) ⁇ 19), an alkoxyalkyl group represented by Formula (III): -C d H 2d O(C e H 2e O) f C g H 2g+1 (III) (wherein d represents a natural number of 1 to 10; e represents a natural number of 1 to 10; f represents a natural number of 0 to 5; and g represents a natural number of 1 to 12, provided that d + e ⁇ f + g ⁇ 20), or a halogenated alkyl group
  • R 1 and R 2 each represent the group represented by Formula (I), ( II), (III), (IV) or (VI).
  • R 1 represents the group represented by Formula (I), (III), (IV) or (VI).
  • the concrete examples of the groups represented by R 1 and R 2 include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicocyl, branched alkyl groups such as 1-methylethyl, 2-methylpropyl, 3-methylbutyl, 4-methylpentyl, 5-methylhexyl, 6-methylheptyl, 7-methyloctyl,
  • A represents any of the groups represented by the following formulas: preferably any of the groups represented by the following formulas:
  • X 1 , X 2 , X 3 and X 4 each represent a hydrogen atom or a halogen atom, preferably a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, more preferably a hydrogen atom, a fluorine atom or a chlorine atom, and further preferably a hydrogen atom or a fluorine atom.
  • the substitution position of X 1 or X 2 is ortho positions or meta positions to the substituent R 1 - or R 1 O-, preferably an ortho position.
  • the substitution position of X 3 is an ortho position or a meta position to a -COO- group, preferably an ortho position.
  • the substitution position of X 4 is an ⁇ -position or ⁇ -position on the naphthalene ring, preferably an ortho position to the substituent R 1 - or R 1 O- and/or a -COO- group, more preferably an ortho position to the substituent R 1 - or R 1 O- and/or a -COO- group, and an ⁇ -position on the naphthalene ring.
  • z represents 0 or 1.
  • naphthalene compounds represented by Formula (1) of the present invention are classified broadly into five kinds of the following structures (1-1) to (1-5):
  • the compound represented by Formula (1) can be produced typically by the following method.
  • the above compound can be produced by carrying out esterification using a compound represented by Formula (3a) and a compound represented by Formula (4): wherein R 1 , R 2 , A and z are synonymous with those described above.
  • Some of the compounds represented by Formula (4) are commercially available. Further, they can be produced by known methods [for example, J. Chem. Soc., 1874 (1935), J. Chem. Soc., 2556 (1954), J. Chem. Soc., 1412 (1955), J. Chem. Soc., 393 (1957) and J. Chem. Soc., 1545 (1959)].
  • a 4-alkoxybenzoic acid derivative can be produced by reacting, for example, a 4-hydroxybenzoic acid derivative with an alkylating agent such as an alkyl halide and an alkyl tosylate in the presence of a base.
  • an alkylating agent such as an alkyl halide and an alkyl tosylate
  • a 4-alkoxybiphenyl-4'-carboxylic acid derivative can be produced by reacting a 4-hydroxybiphenyl-4'-carboxylic acid derivative with an alkylating agent such as an alkyl halide and an alkyl tosylate in the presence of a base.
  • an alkylating agent such as an alkyl halide and an alkyl tosylate
  • the compounds represented by Formulas (3a) or (3b) can be produced typically through the following steps: wherein R 2 is synonymous with that described above; Y represents a halogen atom; and Bz represents a benzyl group.
  • 2-benzyloxy-6-naphthoic acid represented by Formula (5) produced by benzylation of 2-hydroxy-6-naphthoic acid with a benzyl halide is reacted with thionyl chloride or oxalyl chloride to produce an acid halide represented by Formula (6).
  • the acid halide represented by Formula (6) is reacted with an alcoholic compound represented by Formula (7): R 2 - OH (7) wherein R 2 is synonymous with that described above, whereby the compound represented by Formula (3b) can be produced.
  • the compound represented by Formula (3b) can be produced as well by reacting 2-benzyloxy-6-naphthoic acid represented by Formula (5) with the alcoholic compound represented by Formula (7) by the action of a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) in the presence of a catalyst such as, for example, 4-pyrrolidinopyridine and 4-N,N-dimethylaminopyridine.
  • a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC)
  • DCC N,N'-dicyclohexylcarbodiimide
  • a catalyst such as, for example, 4-pyrrolidinopyridine and 4-N,N-dimethylaminopyridine.
  • the compound represented by Formula (3b) can be produced as well by reacting 2-benzyloxy-6-naphthoic acid represented by Formula (5) with an alkylating agent represented by Formula (8) in the presence of an aprotic polar solvent and an alkaline metal salt: R 2 - W (8) wherein R 2 is synonymous with that described above, and W represents a halogen atom or an leaving group such as an arylsulfonyloxy group.
  • the compound represented by Formula (3a) can be produced by hydrogenation (debenzylation) the compound represented by Formula (3b).
  • the hydrogenation can be carried out by known methods. That is, the hydrogenation can be done by carrying out hydrogenation in an organic solvent (for example, alcoholic solvents and ester solvents) at a pressure of atmospheric pressure to about 50 kg/cm 2 in the presence of a catalyst prepared by carrying metals such as, for example, Pd, Pt, Rh, Co and Ni on activated carbon, alumina, barium sulfate, or the like. In general, the hydrogenation is carried out at 0 to 200°C, preferably 10 to 150°C.
  • an organic solvent for example, alcoholic solvents and ester solvents
  • metals such as, for example, Pd, Pt, Rh, Co and Ni on activated carbon, alumina, barium sulfate, or the like.
  • the hydrogenation is carried out at 0 to 200°C, preferably 10 to 150°C.
  • the compound represented by Formula (3a) can be produced as well by reacting 2-hydroxy-6-naphthoic acid with an alkylating agent represented by Formula (8) in the presence of an aprotic polar solvent and an alkaline metal salt.
  • 2-Hydroxy-6-naphthoic acid can be produced by known methods [for example, a method described in J. Chem. Soc., 678 (1954)].
  • the naphthalene compounds represented by Formula (2) that is, the compounds represented by Formula (2a) and (2b) are novel compounds, and the present invention provides these compounds.
  • B 1 represents a hydrogen atom or a benzyl group
  • Bz represents a benzyl group
  • R 3 represents a branched alkyl group having no asymmetric carbon atoms and having 3 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which are substituted with halogen atoms and have no asymmetric carbon atoms, preferably the branched alkyl group represented by Formula (II), the alkoxyalkyl group represented by Formula (III), or the halogenated alkyl group represented by Formula (IV), (V) or (VI), each described above.
  • R 3 there can be given as the concrete examples of R 3 , the branched alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, halogenated alkoxyalkyl groups, and alkenyl groups, each given as the concrete examples of R 1 and R 2 in Formula (1).
  • the naphthalene compounds of the present invention include compounds showing liquid crystallinity in itself and compounds showing no liquid crystallinity in itself. Further, the naphthalene compounds showing liquid crystallinity include compounds showing a smectic C phase and compounds showing liquid crystallinity but no smectic C phase. These compounds each can effectively be used as components for liquid crystal compositions.
  • a liquid crystal composition comprises two or more kinds of components.
  • the liquid crystal composition of the present invention contains at least one naphthalene compound of the present invention as an essential component.
  • the naphthalene compound of the present invention used for the liquid crystal composition of the present invention includes naphthalene compounds showing no liquid crystallinity, compounds showing a smectic C phase, and naphthalene compounds showing liquid crystallinity but no smectic C phase.
  • the liquid crystal composition of the present invention shall not specifically be restricted and includes, for example, liquid crystal compositions showing a smectic phase and liquid crystal compositions showing a chiral smectic phase, preferably liquid crystal compositions showing smectic C, F, G, H and I phases, and liquid crystal compositions showing chiral smectic C, F, G, H and I phases, more preferably liquid crystal compositions showing a chiral smectic C phase.
  • the liquid crystal composition showing a smectic C phase contains at least one compound represented by Formula (1) and can contain, as an optional component, compounds showing a smectic C phase other than the compound represented by Formula (1), for example, liquid crystal compounds such as phenylbenzoate series liquid crystal compounds, biphenylbenzoate series liquid crystal compounds, naphthalene series liquid crystal compounds, phenylnaphthalene series liquid crystal compounds, phenylpyrimidine series liquid crystal compounds, naphthylpyrimidine series liquid crystal compounds and tolan series liquid crystal compounds. Further, a compound showing no smectic C phase in itself may be contained, if desired.
  • the content of at least one compound represented by Formula (1) in the compositions showing smectic C phases shall not specifically be restricted and is usually 1 to 100 weight %, preferably 2 to 80 weight %, and more preferably 2 to 50 weight %.
  • the liquid crystal composition of the present invention showing a chiral smectic C phase comprises at least one compound represented by Formula (1) and further contains as an optically active compound, at least one of known optically active liquid crystal compounds such as optically active phenylbenzoate series liquid crystal compounds, optically active biphenylbenzoate series liquid crystal compounds, optically active naphthalene series liquid crystal compounds, optically active phenylnaphthalene series liquid crystal compounds, optically active phenylpyrimidine series liquid crystal compounds, optically active naphthylpyrimidine series liquid crystal compounds and optically active tolan series liquid crystal compounds.
  • optically active liquid crystal compounds such as optically active phenylbenzoate series liquid crystal compounds, optically active biphenylbenzoate series liquid crystal compounds, optically active naphthalene series liquid crystal compounds, optically active phenylnaphthalene series liquid crystal compounds, optically active phenylpyrimidine series liquid crystal compounds, optically active naphthylpyrimidine series liquid
  • the content of at least one compound represented by Formula (1) in the compositions showing chiral smectic C phases shall not specifically be restricted and is usually 1 to 99 weight %, preferably 2 to 80 weight %, and more preferably 2 to 50 weight %.
  • the liquid crystal composition of the present invention may contain, as an optional component, a compound showing no liquid crystallinity other than the naphthalene compound of the present invention (for example, dichromatic pigments such as anthraquinone pigments and azo pigments, electroconductivity-providing agents, and life improving agents).
  • a compound showing no liquid crystallinity other than the naphthalene compound of the present invention for example, dichromatic pigments such as anthraquinone pigments and azo pigments, electroconductivity-providing agents, and life improving agents.
  • liquid crystal composition of the present invention can provide a liquid crystal element improved in characteristics such as high speed response, temperature dependency of a response time, orientation, a memory property, and contrast ratio.
  • the liquid crystal element of the present invention means a liquid crystal element using a liquid crystal composition containing at least one naphthalene compound represented by Formula (1).
  • the liquid crystal element shall not specifically be restricted and relates preferably to a smectic liquid crystal element, more preferably to a ferroelectric liquid crystal element.
  • liquid crystal compositions showing ferroelectricity cause a switching phenomenon by applying voltage, and liquid crystal elements having a shorter response time can be prepared by making use of the phenomenon [for example, Japanese Patent Application Laid-Open No. 56-107216 (1981), Japanese Patent Application Laid-Open No. 59-118744 (1984), and Appl. Phys. Lett., 36 899 (1980)].
  • the liquid crystal element of the present invention comprises the liquid crystal composition of the present invention disposed between a pair of electrode substrates to form a liquid crystal layer.
  • the liquid crystal layer can be formed by heating the liquid crystal composition under vacuum until it becomes an isotropic solution, injecting it into a liquid crystal cell, then cooling it to form a liquid crystal layer, and restoring pressure in the system to atmospheric pressure.
  • Fig. 1 Shown in Fig. 1 is a schematic, cross-sectional view showing one example of the liquid crystal elements having a chiral smectic phase for explaining the structure of the liquid crystal element making use of ferroelectricity.
  • the liquid crystal element shown in Fig. 1 is a transmitting type liquid crystal element.
  • the form of the liquid crystal element of the present invention shall not specifically be restricted and includes not only a transmitting type liquid crystal element but also, for example, a reflecting type liquid crystal element.
  • 1 represents a liquid crystal (chiral smectic) layer
  • 2 represents a substrate
  • 3 represents a transparent electrode
  • 4 represents an insulating orientation controlling layer
  • 5 represents a spacer
  • 6 represents a lead wire
  • 7 represents a power source
  • 8 represents a polarizing plate
  • 9 represents a light source
  • I 0 represents incident light
  • I represents transmitted light.
  • the liquid crystal element comprises a liquid crystal layer 1 showing a chiral smectic phase disposed between a pair of substrates 2 each of which is provided with a transparent electrode 3 and an insulating orientation controlling layer 4, wherein the layer thickness thereof is controlled by spacers 5, and a power source 7 is connected to a pair of the transparent electrodes 3 via lead wires 6 so that voltage can be applied between the transparent electrodes 3.
  • a pair of the substrates 2 are interposed between a pair of polarizing plates 8 disposed in a cross-nicol state, and a light source 9 is disposed on one outside thereof.
  • a glass substrate or a plastic substrate is used for the substrate 2.
  • the transparent electrodes 3 disposed on two sheets of the substrates 2 include, for example, transparent electrodes comprising thin films of In 2 O 3 , SnO 2 and ITO (indium tin oxide).
  • the materials for the insulating orientation controlling layer 4 include, for example, inorganic materials such as silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and magnesium fluoride, and organic materials such as, for example, polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyparaxylene, polyester, polycarbonate, polyvinylacetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resins, melamine resins, urea resins, acrylic resins and photoresist resins.
  • the insulating orientation controlling layer 4 may be of a dual
  • the insulating orientation controlling layer comprises an inorganic insulating layer
  • it can be formed by deposition.
  • it comprises an organic insulating layer
  • it can be formed by applying a solution dissolving a precursor thereof by spinner coating, dip coating, screen printing, spray coating or roll coating and then curing a resulting film on prescribed curing conditions (for example, heating).
  • the layer thickness of the insulating orientation controlling layer 4 shall not specifically be restricted and is usually a 1 nm to 10 ⁇ m, preferably 1 to 300 nm, more preferably 1 to 100 nm.
  • the substrates 2 are maintained at an optional space with the spacer 5.
  • the substrates can be maintained at an optional space by interposing, for example, silica beads or alumina beads each having a prescribed diameter as the spacer between the substrates 2 and sealing the circumference thereof with sealant (for example, epoxy adhesives). Further, polymer films and glass fibers may be used as the spacers.
  • Liquid crystal showing a chiral smectic phase is charged between two sheets of the substrates.
  • the liquid crystal layer 1 is controlled usually to a thickness of 0.5 to 20 ⁇ m, preferably 1 to 5 ⁇ m.
  • a display system of the liquid crystal element using the liquid crystal composition of the present invention shall not specifically be restricted, and there can be used, for example, display systems of (a) helical distortion type, (b) SSFLC (surface stabilized ferroelectric liquid crystal) type, (c) TSM (transient scattering mode) type and (d) G-H (guest-host) type.
  • the naphthalene compound of the present invention and the liquid crystal composition containing said compound are applicable as well to fields other than liquid crystal elements for display (for example, (1) non-linear photofunctional element, (2) electronics materials such as a condenser material, (3) electronics elements such as a limiter, a memory, an amplifier and a modulator, (4) voltage sensing elements and sensors for heat, light, pressure and mechanical deformation, and (5) power generating elements such as thermoelectric generating element).
  • liquid crystal elements for display for example, (1) non-linear photofunctional element, (2) electronics materials such as a condenser material, (3) electronics elements such as a limiter, a memory, an amplifier and a modulator, (4) voltage sensing elements and sensors for heat, light, pressure and mechanical deformation, and (5) power generating elements such as thermoelectric generating element).
  • Production Example 1 production of n-butyl 2-hydroxy-6-naphthoate
  • Example 2 The same procedure as described in Example 1 was repeated, except that 2-methyl-1-propanol of 8.1 g was substituted for 2-propanol in Example 1, whereby 2'-methylpropyl 2-benzyloxy-6-naphthoate of 30.1 g was obtained in the form of colorless crystal. Melting point: 114.0 to 115.5°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 3-methyl-1-butanol of 9.7 g was substituted for 2-propanol in Example 1, whereby 3'-methylbutyl 2-benzyloxy-6-naphthoate of 31.0 g was obtained in the form of colorless crystal. Melting point: 89.5 to 91.0°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 4-methyl-1-pentanol of 11.2 g was substituted for 2-propanol in Example 1, whereby 4'-methylpentyl 2-benzyloxy-6-naphthoate of 29.0 g was obtained in the form of colorless crystal. Melting point: 64.0 to 67.0°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 3-pentanol of 9.7 g was substituted for 2-propanol in Example 1, whereby 1'-ethylpropyl 2-benzyloxy-6-naphthoate of 26.1 g was obtained in the form of colorless crystal. Melting point: 65.0 to 70.0°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 2-ethyl-1-butanol of 11.2 g was substituted for 2-propanol in Example 1, whereby 2'-ethylbutyl 2-benzyloxy-6-naphthoate of 31.7 g was obtained in the form of colorless crystal. Melting point: 84.0 to 86.0°C.
  • Example 7 production of 1',1',5'-trihydroperfluoro-n-pentyl 2-benzyloxy-6-naphthoate
  • Example 2 The same procedure as described in Example 1 was repeated, except that 1,1,5-trihydroperfluoro-n-pentyl alcohol of 25.5 g was substituted for 2-propanol in Example 1, whereby 1',1',5'-trihydroperfluoro-n-pentyl 2-benzyloxy-6-naphthoate of 38.4 g was obtained in the form of colorless crystal. Melting point: 98.0 to 100.0°C.
  • Example 8 production of 1',1',7'-trihydroperfluoro-n-heptyl 2-benzyloxy-6-naphthoate
  • Example 2 The same procedure as described in Example 1 was repeated, except that 1,1,7-trihydroperfluoro-n-heptyl alcohol of 36.5 g was substituted for 2-propanol in Example 1, whereby 1',1',7'-trihydroperfluoro-n-heptyl 2-benzyloxy-6-naphthoate of 39.4 g was obtained in the form of colorless crystal. Melting point: 108.0 to 112.0°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 2-(perfluoro-n-butyl)ethanol of 51.6 g was substituted for 2-propanol in Example 1, whereby 2'-(perfluoro-n-butyl)ethyl 2-benzyloxy-6-naphthoate of 63.4 g was obtained in the form of colorless crystal. Melting point: 108.0 to 109.0°C.
  • Example 2 The same procedure as described in Example 1 was repeated, except that 2-(perfluoro-n-hexyl)ethanol of 40.0 g was substituted for 2-propanol in Example 1, whereby 2'-(perfluoro-n-hexyl)ethyl 2-benzyloxy-6-naphthoate of 52.4 g was obtained in the form of colorless crystal. Melting point: 115.0 to 117.0°C.
  • Example 11 The same procedure as described in Example 11 was repeated, except that 2-n-hexyloxyethyl p-toluenesulfonate of 45.0 g was substituted for 2-n-butoxyethyl p-toluenesulfonate in Example 11, whereby 2'-n-hexyloxyethyl 2-benzyloxy-6-naphthoate of 28.4 g was obtained in the form of colorless oily substance.
  • Example 11 The same procedure as described in Example 11 was repeated, except that 2-(2'-n-hexyloxyethoxy)ethyl p-toluenesulfonate of 51.6 g was substituted for 2-n-butoxyethyl p-toluenesulfonate in Example 11, whereby 2'-(2"-n-hexyloxyethoxy)ethyl 2-benzyloxy-6-naphthoate of 29.3 g was obtained in the form of colorless oily substance.
  • Example 11 The same procedure as described in Example 11 was repeated, except that 2-[2'-(2"-n-butoxyethoxy)ethoxy]ethyl p-toluenesulfonate of 54.0 g was substituted for 2-n-butoxyethyl p-toluenesulfonate in Example 11, whereby 2'-[2"-(2"'-n-butoxyethoxy)ethoxy]ethyl 2-benzyloxy-6-naphthoate of 35.6 g was obtained in the form of colorless oily substance.
  • 1'-methylethyl 2-benzyloxy-6-naphthoate of 16.0 g was dissolved in 2-propanol of 100 g and hydrogenated at 40°C in a hydrogen atmosphere at atmospheric pressure in the presence of 5 weight % Pd/C of 1 g. Pd/C was filtered off, and then 2-propanol was distilled off under reduced pressure, whereby 1'-methylethyl 2-hydroxy-6-naphthoate of 10.2 g was obtained in the form of colorless crystal. Melting point: 110.0 to 114.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-methylpropyl 2-benzyloxy-6-naphthoate of 16.7 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-methylpropyl 2-hydroxy-6-naphthoate of 10.7 g was obtained in the form of colorless crystal. Melting point: 112.5 to 123.5°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 3'-methylbutyl 2-benzyloxy-6-naphthoate of 17.4 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 3'-methylbutyl 2-hydroxy-6-naphthoate of 12.3 g was obtained in the form of colorless crystal. Melting point: 119.5 to 121.5°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 4'-methylpentyl 2-benzyloxy-6-naphthoate of 18.1 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 4'-methylpentyl 2-hydroxy-6-naphthoate of 11.6 g was obtained in the form of colorless crystal. Melting point: 73.0 to 74.5°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 1'-ethylpropyl 2-benzyloxy-6-naphthoate of 17.4 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 1'-ethylpropyl 2-hydroxy-6-naphthoate of 11.6 g was obtained in the form of colorless crystal. Melting point: 89.0 to 92.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-ethylbutyl 2-benzyloxy-6-naphthoate of 18.1 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-ethylbutyl 2-hydroxy-6-naphthoate of 12.8 g was obtained in the form of colorless crystal. Melting point: 96.5 to 97.5°C.
  • Example 21 production of 1',1',5'-trihydroperfluoro-n-pentyl 2-hydroxy-6-naphthoate
  • Example 15 The same procedure as described in Example 15 was repeated, except that 1',1',5'-trihydroperfluoro-n-pentyl 2-benzyloxy-6-naphthoate of 24.6 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 1',1',5'-trihydroperfluoro-n-pentyl 2-hydroxy-6-naphthoate of 17.5 g was obtained in the form of colorless crystal. Melting point: 105.0 to 113.0°C.
  • Example 22 production of 1',1',7'-trihydroperfluoro-n-heptyl 2-hydroxy-6-naphthoate
  • Example 15 The same procedure as described in Example 15 was repeated, except that 1',1',7'-trihydroperfluoro-n-heptyl 2-benzyloxy-6-naphthoate of 29.6 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 1',1',7'-trihydroperfluoro-n-heptyl 2-hydroxy-6-naphthoate of 20.1 g was obtained in the form of colorless crystal. Melting point: 123.0 to 132.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-(perfluoro-n-butyl)ethyl 2-benzyloxy-6-naphthoate of 26.2 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-(perfluoro-n-butyl)ethyl 2-hydroxy-6-naphthoate of 18.6 g was obtained in the form of colorless crystal. Melting point: 101.0 to 103.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-( perfluoro-n-hexyl)ethyl 2-benzyloxy-6-naphthoate of 31.2 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-(perfluoro-n-hexyl)ethyl 2-hydroxy-6-naphthoate of 21.4 g was obtained in the form of colorless crystal. Melting point: 124.0 to 127.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-n-butoxyethyl 2-benzyloxy-6-naphthoate of 18.9 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-n-butoxyethyl 2-hydroxy-6-naphthoate of 13.7 g was obtained in the form of colorless crystal. Melting point: 54.0 to 56.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-n-hexyloxyethyl 2-benzyloxy-6-naphthoate of 20.3 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-n-hexyloxyethyl 2-hydroxy-6-naphthoate of 15.0 g was obtained in the form of colorless crystal. Melting point: 67.0 to 68.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-(2"-n-hexyloxyethoxy)ethyl 2-benzyloxy-6-naphthoate of 22.5 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-(2"-n-hexyloxyethoxy)ethyl 2-hydroxy-6-naphthoate of 15.3 g was obtained in the form of colorless crystal. Melting point: 59.0 to 62.0°C.
  • Example 15 The same procedure as described in Example 15 was repeated, except that 2'-[2"-(2′′′-n-butoxyethoxy)ethoxy]ethyl 2-benzyloxy-6-naphthoate of 23.3 g was substituted for 1'-methylethyl 2-benzyloxy-6-naphthoate in Example 15, whereby 2'-[2"-(2"'-n-butoxyethoxy)ethoxy]ethyl 2-hydroxy-6-naphthoate of 14.2 g was obtained in the form of colorless oily substance.
  • the crude product was refined with silica gel column chromatography (eluent: toluene) and further recrystallized twice from ethanol/ethyl acetate, whereby the intended product of 392 mg was obtained in the form of colorless crystal.
  • phase transition temperatures of this compound are shown in Table 2.
  • naphthalene compounds were produced in the same manner as described in Example 29, except that 2-hydroxy-6-naphthoic acid esters represented by Formula (3a) and various carboxylic acids represented by Formula (4), each shown in Table 1, were used.
  • phase transition temperatures of these compounds are shown in Table 2.
  • Example 115 preparation of liquid crystal composition
  • liquid crystal composition A ferroelectric liquid crystal composition
  • composition A Composition A
  • Transparent electrodes and insulating orientation controlling layers made of polyimide were provided on two glass plates having a thickness of 0.7 mm, and alumina beads having an average particle diameter of 2 ⁇ m were dispersed on one of the glass plates. Then, the glass plates were stuck together with sealant to prepare a cell shown in Fig. 1. This cell was charged with the liquid crystal composition prepared above after heating it to be in an isotropic phase, and the liquid crystal composition was gradually cooled down to be in a ferroelectric liquid crystal phase at a rate of 1°C/minute, whereby a liquid crystal element was prepared.
  • This liquid crystal element was interposed between two polarizing plates disposed in a cross-nicol state, and was applied a voltage of 20 V to detect an optical response (change in a transmitted light quantity: 10 to 90 %), whereby the response time was determined.
  • the measured results are shown in Fig. 2.
  • Example 116 preparation of liquid crystal composition
  • liquid crystal composition B ferrroelectric liquid crystal composition
  • Transparent electrodes and insulating orientation controlling layers made of polyimide were provided on two glass plates having a thickness of 0.7 mm, and alumina beads having an average particle diameter of 2 ⁇ m were dispersed on one of the glass plates. Then, the glass plates were stuck together with sealant to prepare a cell shown in Fig. 1. This cell was charged with the liquid crystal composition prepared above after heating it to be in an isotropic phase, and the liquid crystal composition was gradually cooled down to be in a ferroelectric liquid crystal phase at a rate of 1°C/minute, whereby a liquid crystal element was prepared.
  • This liquid crystal element was interposed between two polarizing plates disposed in a cross-nicol state, and was applied a voltage of 20 V to detect an optical response (change in a transmitted light quantity: 10 to 90 %), whereby the response time was determined.
  • the measured results are shown in Fig. 2.
  • liquid crystal composition C ferrroelectric liquid crystal composition
  • Transparent electrodes and insulating orientation controlling layers made of polyimide were provided on two glass plates having a thickness of 0.7 mm, and alumina beads having an average particle diameter of 2 ⁇ m were dispersed on one of the glass plates. Then, the glass plates were stuck together with sealant to prepare a cell shown in Fig. 1. This cell was charged with the liquid crystal composition prepared above after heating it to be in an isotropic phase, and the liquid crystal composition was gradually cooled down to be in a ferroelectric liquid crystal phase at a rate of 1°C/minute, whereby a liquid crystal element was prepared.
  • This liquid crystal element was interposed between two polarizing plates disposed in a cross-nicol state, and was applied a voltage of 20 V to detect an optical response (change in a transmitted light quantity: 10 to 90 %), whereby the response time was determined.
  • the measured results are shown in Fig. 2.

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US6720039B1 (en) 1997-02-19 2004-04-13 Dai Nippon Printing Co., Ltd. Liquid crystalline compounds and process for producing the same

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US6870163B1 (en) 1999-09-01 2005-03-22 Displaytech, Inc. Ferroelectric liquid crystal devices using materials with a de Vries smectic A phase
US7083832B2 (en) 2000-09-01 2006-08-01 Displaytech, Inc. Partially fluorinated liquid crystal material
US7195719B1 (en) 2001-01-03 2007-03-27 Displaytech, Inc. High polarization ferroelectric liquid crystal compositions
US6703082B1 (en) 2001-06-20 2004-03-09 Displaytech, Inc. Bookshelf liquid crystal materials and devices
US6838128B1 (en) 2002-02-05 2005-01-04 Displaytech, Inc. High polarization dopants for ferroelectric liquid crystal compositions
US20160057859A1 (en) * 2014-08-21 2016-02-25 Juan José de Miguel Electron spin filter

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EP0860417A3 (fr) * 1997-02-19 1999-07-28 Dai Nippon Printing Co., Ltd. Composés liquides cristallins et procédé de préparation
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